Preparation of oligomeric cyclocarbonates and their use in ionisocyanate or hybrid nonisocyanate polyurethanes

ABSTRACT

A method and apparatus for synthesis of oligomeric cyclocarbonates from epoxy compounds and carbon dioxide in the presence of a catalyst. Star epoxy compounds and their preparation and use in making star cyclocarbonates, star hydroxy urethane oligomers, and star NIPU and HNIPU. Acrylic epoxy compounds, acrylic cyclocarbonates, acrylic hydroxy urethane oligomers, and acrylic NIPU and HNIPU and their methods of preparation.

FIELD OF THE INVENTION

The present invention generally relates to the preparation of oligomericcyclocarbonates and their use in nonisocyanate polyurethanes (NIPU) andhybrid nonisocyanate polyurethanes (HNIPU). In particular, the presentinvention relates to an improved method of and apparatus for synthesisof oligomeric cyclocarbonates from epoxy compounds and carbon dioxide.The present invention further relates to the novel star and acryliccyclocarbonate compounds and their use in novel star and acrylic hydroxyurethane oligomers and novel star and acrylic NIPU and HNIPUcompositions.

BACKGROUND OF THE INVENTION

Nonisocyanate polyurethane materials differ completely, both instructure and in properties, from polyurethanes produced from isocyanatecontaining oligomers and/or starting materials.

Prior art methods of producing polyurethane compounds that rely upon thereaction of terminated hydroxyl groups with terminated isocyanate groupsrequires the use of toxic starting materials such as isocyanates andcompeting side-reactions during production generates gases that resultin an undesirable highly porous material. Furthermore, polyurethanesderived from isocyanates have hydrolytically unstable chemical bondrendering them highly susceptible to environmental degradation.

These problems can be overcome by making of a polyurethane without theuse of toxic isocyanates, thus creating a modified polyurethane withlower permeability and increased chemical resistance properties toaqueous solutions of acids and alkalis.

We previously discovered and disclosed in U.S. Pat. No. 6,120,905 toFigovsky, the structure of hybrid nonisocyanate polyurethane networkpolymers, composite formed therefrom, and their synthesis. Thesepolyurethanes are formed by a reaction of cyclocarbonates with primaryamine polyfunctional oligomers. Our prior patented process carries outthe cyclocarbonate-oligomer synthesis in thin film reactor at atemperature of 65 to 105° C., and at the pressure of about 6.0 to 8.5atm for about 190 to 330 minutes. The resultant product contains notonly terminated cyclocarbonate-groups but also terminated epoxy groups.We have subsequently found this process to have a very small capacityand yields cyclocarbonate-oligomer with yellow color, which is notsuitable for use with clear coats and other products requiring a clearor white color.

Urethane oligomers can be prepared, as shown in U.S. Pat. No. 5,175,231to Rappoport et al., by reacting a compound containing a plurality ofcyclocarbonate groups with a diamine where the amine groups havedifferent reactivities with cyclocarbonate, so as to form urethaneoligomer with amine terminated groups. The amino-oligomer is used as ahardener of epoxy resin and can be cross-linked by reacting it with anepoxy resin to form a network structure. The cyclocarbonates aresynthesized from epoxy resins and carbon dioxide in the presence ofcatalyst in a reactor under pressure 130-150 psi (8.9-10.3 bar) andelevated temperature 240° F. (150° C.). In the Rappoport et al. process,carbon dioxide is introduced in the bottom of the reactor previouslyloaded with epoxy compound and catalyst. The conversion of epoxy groupsto cyclocarbonate groups is strongly dependent upon the saturation ofthe epoxy compound by the carbon dioxide. In the Rappoport et alprocess, despite vigorous stirring that generates a foam, the reactionstill takes several hours and requires the use of high temperatures,high pressures, large amounts of catalyst and long reaction times, toavoid having a significant amount of unreacted epoxy groups that reducethe concentration of the urethane groups and the number of hydrogenatedlinks in the final polyurethane network. Unfortunately, althoughRappoport et al. are able to ensure that nearly all the epoxy groupshave been turned into cyclocarbonate groups in this reaction, they alsoend up producing undesirable side reactions and products, while beingmore expensive and time-consuming.

Other efforts to create such nonisocyanate polyurethanes have hadfurther problems. U.S. Pat. No. 4,758,615 to Engel Dieter, et al.discloses the process of synthesis of polymers containing nonisocyanateurethane groups by reacting polyamino compounds with polycarbonates andreacting the reaction product further with polycarboxylic acids forpreparing aqueous polymer dispersions.

Production of other nonisocyanate polyurethanes based on the reactionbetween the oligomeric bifunctional cyclocarbonate oligomers and aminesare disclosed by U.S. Pat. No. 5,340,889 to Crawford et al. In thisprocess, liquid hydroxyurethane products are prepared by reacting amolar excess of bis-carbonate of a bis-glycidyl ether of neopentylglycol or 1,4-cyclo-hexanedimenthanol with polyoxyalkylenediamine.However, the resultant polyurethanes lack a cross-linked networkstructure, and thus are not chemically resistant and also are notsuitable for construction and structural materials.

The reaction of cyclocarbonates with amine compounds can result inproducts other than polyurethanes. For example, USSR InventorsCertificate No. 1353792 to Danilova, et al. discloses reacting anepoxy-cyclocarbonate resin, urea formaldehyde, triazine resin and aminehardener to prepare an adhesive composition. And U.S. Pat. No. 4,585,566to Wollenberg discloses the process of synthesis of dispersants byreaction of a primary or secondary amino group with mono-cycliccarbonate.

The tensile strength and deformation properties of nonisocyantepolyurethanes are comparable with standard isocyanate polyurethanes, butthe nonisocyanate polyurethanes do not have pores, and thus are notsensitive to moisture in the surrounding environment. The mainproperties of nonisocyanate polyurethanes depend on the structure andthe functionality of the cyclocarbonate and amine oligomers from whichit is made.

As noted above, the known reactions for preparing nonisocyanatepolyurethanes by using cyclocarbonates and primary amines areproblematic in that the reaction stops before the process is completedresulting in an incompletely hardened network polymer that adverselyaffects the properties of network polymer. Although attempts have beenmade to prepare and add hardeners for epoxy resin, such as shown in U.S.Pat. No. 5,175,231, they have not is been successful in increasing thedesirable properties of the nonisocyanate polyurethanes.

The preparation of cyclocarbonates has also been fraught withdifficulties and products unsuitable for use in further processing intononisocyanate polyurethanes. For example the process disclosed in U.S.Pat. No. 5,817,838 to Gründler et al. prepares cyclocarbonates fromepoxides and carbon dioxide in the presence of a quanternary ammonium orphosphonium salt with a further silver salt catalyst to assist thereaction process. However, the use of the silver salt catalyst resultsin a material that is unacceptably dark in color.

Other processes for the preparation of cyclocarbonates require the useof high reactor temperatures despite the use of various types ofcatalysts. For example, U.S. Pat. No. 5,153,333 uses quaternaryphosphonium compounds as a catalyst, but still requires reactortemperatures of 200° C. U.S. Pat. No. 4,835,289 uses alkali iodides andreactor temperatures of 180° C.

SUMMARY OF THE INVENTION

The present invention is directed to an improved method of synthesis ofoligomeric cyclocarbonates from digomeric epoxides and carbon dioxide inthe presence of a catalyst in a reactor or cascade of reactors and theapparatus therefore. The improved method allows the reaction to progressto completion at low temperatures and low pressures for short timeperiods without side reactions and the production of byproducts.

The invention is further directed to NIPU and HNIPU with improvedproperties and the compositions from which they are produced.

In particular, the invention is directed to a highly functionalized starepoxy compounds, star cyclocarbonates, star hydroxy urethane oligomers,and star NIPU and HNIPU, as well as to and their method of preparation.

The present invention is also directed to an acrylic epoxy compounds, anacrylic polymer with pendant cyclocarbonate groups, an acrylic backbonehydroxy urethane oligomers, and acrylic backbone NIPU and HNIPU andtheir methods of preparation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a schematic representation of a turbine mixing device reactorin which the improved method of the present invention is conducted;

FIG. 1B is a cross section of the turbine mixer blade of FIG. 1 taken online 1B;

FIG. 2A is a schematic representation of one embodiment of the reactionto produce network nonisocyanate polyurethanes (NIPU):

FIG. 2B is a schematic representation of another embodiment is of thereaction to produce NIPU;

FIG. 3 is a schematic representation of an embodiment of the reaction toproduce hybrid network nonisocyanate polyurethanes (HNIPU);

FIG. 4 is a schematic representation of an embodiment of the reaction toproduce hydroxyurethane oligomer with increased functionality (HUOIF);

FIG. 5 is a schematic representation of another embodiment of thereaction to produce epoxy oligomer with increased functionality (EOIF);

FIG. 6 is a schematic representation of another embodiment of thereaction to produce aminohydroxyurethane oligomer with increasedfunctionality (AHUOIF);

FIG. 7 is a Table showing the results of Examples 1-6 as compared to theprior art;

FIG. 8 is a Table showing the network polyurethane properties ofExamples 7-9 relative to a control and to the prior art; and

FIG. 9 depicts the formula for a reactant used to make a cyclocarbonateterminated “star” oligomer of increased functionality.

DETAILED DESCRIPTION OF THE INVENTION

The synthesis of nonisocyanate network polyurethanes and hybridnonisocyanate network polymers involves a number of stages. The firststage is the preparation of a cyclocarbonate from the reaction of anepoxy or epoxide with carbon dioxide. The resultant cyclocarbonate isreacted with an amine containing compound to form an hydroxy urethaneoligomer. The hydroxy urethane oligomer is then cross linked to form anonisocyanate network polyurethane (NIPU) or a hybrid nonisocyanatenetwork polyurethane (HNIPU). The properties of the resultant NIPU orHNIPU depend upon the properties of the cyclocarbonate and amineoligomers from which it is produced.

Others in the art have had problems with obtaining NIPU and HNIPU withthe desired properties due to many factors, including the problems withobtaining a cyclocarbonate material of sufficient purity.

Accordingly, the present invention is directed to an improved method andapparatus for the preparation of cyclocarbonates from epoxides and epoxycontaining compounds by reaction with carbon dioxide. The invention isfurther directed to the preparation of novel highly functionalized starcyclocarbonate and novel acrylic backbone polymers with pendantcyclocarbonate groups and the use of such novel compounds in thepreparation of novel hydroxy urethane oligomers and novel NIPU and HNIPUcompositions.

In prior reaction systems, as described above, carbon dioxide isintroduced into the bottom of a reactor vessel and reacts with theepoxide as it upwardly traverses the reaction mass. To ensure that thereaction proceeds, it is necessary to use high pressures of carbondioxide, as well as high temperatures, long reaction times, andcatalysts. All of these degrade the resultant product requiringseparation and purification steps before the cyclocarbonate product canbe used.

The improved process of the present invention utilizes a reactor thatmaximizes the surface contact area between the reactionary epoxide massand the carbon dioxide, thus obviating the need for high temperatures,high pressures, and long reaction times. In the process of the presentinvention, the saturation of reaction mass by carbon dioxide ismaximized by both feeding the carbon dioxide to the head space above thereaction mixture and feeding the carbon dioxide directly into thereaction mass by means of a turbine mixing device with a gas entrainmentimpeller.

The process can best be understood by reference to FIG. 1A, which showsa reaction vessel 5 having a diameter d₃ in which the epoxide is chargedto form reaction mass 1 having a height H₁. Carbon dioxide is introducedby means of inlet 4 into the head space above the reaction mixture 1.Carbon dioxide is also fed by means of a gas turbine mixer whichcomprising a hollow shaft 3 in fluid communication with hollow gasentrainment impeller 6 that feed the carbon dioxide by means of gasoutlets 7 directly into the reaction mixture 1 while rotating. Thehollow shaft 3 has an inside diameter of d₂ and contains inlet ports ofopenings 2, each with a diameter of d₄, that permit the carbon dioxidegas to continuously recirculate from the head space above the reactionmass 1 directly into the reaction mass 1. The carbon dioxide gas entersnear the top of the hollow shaft 3 through openings 2 and is drawnthrough the hollow shaft 3 and through hollow gas entrainment impeller 6having a height H₂ and is then the expelled through dispersion ports oroutlets 7 located at the tip of the impeller 6. The dispersion ports oroutlets each have a diameter of d₅. The diameter of the impeller 6, asmeasured from tip to tip, is denoted by d₁. The impeller is located adistance h from the bottom of the reactor 5. The rotation of theimpeller 6 creates a vacuum at the tip of impeller where the dispersionports or outlets 7 are located. The speed of rotation is directlyrelated to the vacuum created, and thus the driving force for thedispersion of the carbon dioxide gas into the reaction mass 1, with thehigher the speed, the higher the vacuum, and the higher the drivingforce.

In a preferred embodiment of the invention, the ratio of the insidediameter d₂ of shaft 3 to the largest diameter d₁ of the turbine mixingdevice measured from tip of impeller to tip of impeller as shown in FIG.1B is preferably in the range of about 1:4 to about 1:6, with a range of1:4 the most preferred.

In another preferred embodiment, the ratio of the sum of the square ofthe diameter d₄ of the inlet ports 2 on the hollow shaft 3 to the sum ofthe square of outlet ports d₅ as shown in FIG. 1B is preferably fromabout 1:3 to about 1:4. (Σd₄:Σd₅ FIG. 1).

In yet another preferred embodiment of the invention, the ratio of theheight H₂ of impeller 7 to the height H₁ of mixing layer or reactionmass 1 is preferably from about 1:2 to about 1:4.

The synthesis of cyclocarbonates can be carried out in a single reactorin a batch wise process or in a series or cascade of reactors on acontinuous action basis. When a cascade of reactors is used, acyclocarbonate product of extremely great purity can be obtained.

The reaction is conducted in the presence of a suitable catalyst, whichare well-known to those of skill in the art, and include quaternaryammonium salts, quaternary phosphonium salts, quaternary arseniurmsalts, alkali metal halides of Cl, Br, I, and the like.

The reaction is preferably conducted at a temperature of about 70-180°C. and a pressure of at least one atmosphere, preferably from about 1-15bar. For a clearer product, lower temperatures are preferred.

This reaction system has unexpectedly been found to have excellentgas-liquid contact without the generation of foam. Furthermore, due tothe excellent gas-liquid contact made in this reactor, the reaction timeis greatly reduced, generally by a factor of 2 to 4, over other knownsystems. For example, under identical conditions of temperature andpressure, the present system requires only 40 to 120 minutes forreaction, while that shown in U.S. Pat. No. 5,175,231 requires at leasta time period of 180 minutes.

We have also found that this reaction system permits a gentle reactionwithout the use of harsh conditions that result in the production ofundesired byproducts and side reactions.

The present invention further relates to the preparation of novelnetwork nonisocyanate polyurethanes using the novel synthesizedcyclocarbonates of the present invention. In one embodiment of theinvention, the novel synthesized cyclocarbonates are star carbonates ofincreased functionality. In another embodiment, the novel synthesizedcyclocarbonates are acrylic polymers with pendant cyclocarbonate groups.

Functionality, also referred to as “f”, refers to the number of reactivecenters and is calculated from the structural formula. Thus, an epoxyterminated oligomer would have two epoxy groups, and thus afunctionality of 2. If it is reacted in accordance with the presentinvention as shown in FIG. 5, the resultant star epoxy oligomer wouldhave a functionality of 4.

The star oligomers of the present invention refer to oligomers is withmultiple functional groups that have been linked together using onefunctional group from each oligomer to form a linkage, such as anhydroxyurethane linkage, to form a polymer with increased functionality.This linkage process can be used to create a star polymer of any desiredfunctionality. Generally a functionality of about 2 to about 6 ispreferred, and more preferably about 3 to about 5, as too great of anincrease in functionality can hinder the use of the star oligomer inpreparation of desired products such as network nonisocyantepolyurethanes.

For example, a star-epoxy oligomer is a product of the reaction betweenan oligomer with terminated epoxy groups (by functionality not less than1.99) and amino oligomer with primary amino groups (by functionality noless than 1.99) so that one terminated epoxy group from one oligomer andone terminated epoxy group from another oligomer both react with theamino oligomer to form an hydroxyurethane linkage connecting the twoepoxy oligomers together to form a star epoxy oligomer. See for exampleFIG. 5 which shows the reaction of 4 epoxy oligomers to form a starepoxy oligomer of functionality 4, i.e. 4 unreacted epoxy groupsremaining.

In one embodiment of the invention, the network nonisocyanatepolyurethanes (NIPU) of this invention are prepared by an improvedmethod by interaction in situ of at least one cyclocarbonatehydroxyurethane “star” oligomer (star cyclocarbonate oligomer) withincreased functionality (f≧3) and having terminated cyclocarbonategroups and at least two hydroxyurethane linkage groups withamino-oligomer containing at least two terminated primary amino groupswith at least two hydroxyurethane groups. See FIG. 2A.

In another embodiment of the invention, the network nonisocyanatepolyurethanes are prepared by interaction of “star” oligomer withterminated amino groups (FIG. 6) with oligomer containing epoxy groups.(functionality f≧2). The network hybrid nonisocyanate polyurethanes areprepared. See FIG. 2B.

In another embodiment of the invention, the network nonisocyanatepolyurethanes are prepared by interaction of “star” oligomer withterminated amino groups (FIG. 6) and epoxy oligomer with increasedfunctionality (EOIF) (FIG. 5).

In another embodiment of the invention, “star” hydroxyurethane oligomerwith increased functionality (HUOIF) is synthesized by reacting n molesof oligomer, containing terminated cyclocarbonate groups(functionality≧3), and m moles of amines, wherein n>m. See FIG. 4.

In another embodiment of the invention, “star” hydroxyurethane oligomerwith increased functionality (HUOIF) is synthesized by reacting n molesof oligomer, containing terminated cyclocarbonate groups(functionality≧3), and m moles of amines, where n>m. See FIG. 5.

In another embodiment of the invention, “star” hydroxylamino oligomerwith increased functionality (AHUOIF) with terminated amino groups issynthesized by interaction of n moles of HUOIF (functionality f≧3) and mmoles of primary diamines where m≧f. See FIG. 6.

In a further embodiment of the invention, the star polymers are multi orpolyfunctional polymers can contain a multiplicity of different types offunctional groups. For example, the star epoxy oligomer may have epoxy,cyclocarbonate, amine and other groups, not just the epoxy groups.

In yet another embodiment of the invention, acrylic epoxides in the formof an acrylic backbone polymers with pendant epoxide groups, are used toproduce novel acrylic cyclocarbonate oligomers. The novel acryliccyclocarbonate oligomers are reacted with primary amines, diamines andtertiary amines to form a novel acrylic aminohydroxyurethane that can becured to form an acrylic NIPU or HNIPU. Polyfunctional acrylic oligomersknown to those skilled in the art can be used in the present invention.For example, copolymers of acrylic monomers methylmethacrylate,butylacrylate, 1-methacrylate-2,3-epoxy, and the like can be used. Anexample of such a polyfunctional acrylic oligomer is

The novel star and acrylic NIPU and HNIPU compositions of the presentinvention can take any suitable form and the oligomers from which it ismade can be selected to provide the desired properties such as gloss,degree of hardness, flexibility, UV stability, abrasion resistance,weathering resistance and the like. From this disclosure, one of skillin the art would be able to make an appropriate selection of materialswithout undue experimentation.

Due to their superior structure and excellent resistance to degradation,the novel star and acrylic NIPU and HNIPU compositions of the presentinvention are useful for numerous applications including crack resistantcomposite materials, chemically resistant coatings, sealants, glues,paints and the like. These novel compositions are useful in a host ofindustries. For example, uses in the automotive industry includebumpers, dashboards, inhibiting sealants, paints, plastics, repairputty, seating, steering wheels, trim components, truck beds, and thelike. Aerospace uses include airplane and rocket sealants, interiorcomponents, seating, syntactic non-burning foam, and the like. Uses inthe construction industry are myriad and include adhesives, coatings,coverings, crack barrier concrete, elastomers, epoxy resin hardeners,exterior wallboard, flooring, foams, glues, metals, plastics, plywood,rooftops, sealants, wood coatings, and the like. Industrial uses includecoatings, paints and sealants for heavy industrial equipment, machinery,molded parts, and the like. The novel compositions are particularly wellsuited for marine environments and can be used for bridge decks,coatings, interior and exterior components, paints, sealants and thelike. Other possible uses include appliances, footwear, furniture,plastics, synthetic leather, toys, and the like.

These novel compositions are particularly useful as coatings and paintsand can be used as coatings on industrial machines, as floor coatings,as coatings and paints for automobiles, trucks, and buses, as coatingsand paints on outdoor structures such as bridges and trusses, ascoatings and paints on interior structural members such as trusses,ceilings, walls, and the like.

By selection of the oligomers used in preparation of these novelcompositions, one skilled in the art can provide a liquid paint orcoating composition containing these novel compositions that issprayable with conventional paint equipment, has a potlife of sufficienttime, has reduced VOC, and suitable cure times. The resultant curedcoatings have a desired gloss, hardness, adhesion, impact resistance,corrosion resistance, humidity resistance, chemical resistance, andweathering resistance.

In a further embodiment of the present invention, these novel star andacrylic NIPU and HNIPU compositions can be foamed using a blowing agentsuch as pentane to provide a foamed coating composition.

The present invention provides structures, which solve the problem ofincreasing of the mechanical properties of NIPU and HNIPU.

Since the present reaction does not require the use of highly toxicmaterials, it is possible to perform the reaction without specialequipment.

In general, the synthesis of nonisocyanate network polyurethanes of thepresent invention is conducted as follows:

The First Stage.

Any suitable epoxy compound known to one skilled in the art can bereacted with carbon dioxide to form the corresponding cyclocarbonates.The reaction can be conducted in either a batch-process (single reactor)or in a continuous process (cascade or series of reactors) in thepresence of a suitable catalyst well-known to those of skill in the art.Examples of suitable catalysts include quaternary ammonium salts,quaternary phosphonium salts, quaternary arsenium salts, alkali metalhalides (Cl, Br, I) and the like of alkali metal. In a preferredembodiment of the invention, the reactor temperature is 70-180° C. andpressure 1-15 bar is supported.

The carbon dioxide is fed to the upper part of the reactor, from whichit is fed by the turbine mixing device (gas entrainment impeller)directly in to the reactionary mass.

Due to the dispersion effects of the turbine mixing device which resultin a “soaking up” of the carbon dioxide by the reactionary mass, thecarbon dioxide is entered into the reactionary mix throughout the entireworking volume of the reactionary mass and thus raises saturation ofepoxy compounds by the carbon dioxide enabling the reaction to becompleted in a significantly shorter time than in the prior art devicesutilizing periodic action under pressure. It provides faster andcomplete production of cyclocarbonate, with the reaction of the presentinvention being 2 to 4 times faster than that in the prior art.

EXAMPLE 1

A reactor of the type depicted in FIG. 1 is used to efficiently preparecyclocarbonates.

500 grams of epoxy resin D.E.R.-324 (Dow Chemical) were mixed with thecatalyst tetrabutylammonium bromide (C₄H₉) ₄NBr in quantity 0.5% ofweight of epoxy and loaded into the reactor (volume—1 liter). Carbondioxide was fed for a period of 45 minutes through the hollow shaft andout the holes at the ends of the impeller into the epoxy/catalystmixture. The initial reactor conditions were a temperature of 70° C.,and a pressure of 8 bar, at which point absorption of the carbon dioxidecommenced. The reaction was exothermic, and finished at a temperature of120° C. The mean velocity of absorption CO₂ during the reaction was 2.4grams per minute.

The reaction resulted in the preparation of 580 grams of acyclocarbonate oligomer containing 35% cyclocarbonate groups and 0.3%epoxy groups. Conversion was 99%.

EXAMPLE 2

Using the procedure of Example 1, 620 grams epoxy resin Oksilin-6B(Russia) were mixed with the catalyst tetrabutylammonium bromide (C₄H₉)₄NBr in quantity 0.5% of weight of epoxy and loaded into the reactor(volume—1 liter). Carbon dioxide was fed to the reactor for a period of40 minutes through the hollow shaft and out of the holes in the impellerinto the epoxy/catalyst mixture. The initial reactor conditions were atemperature of 70° C. and a pressure of 8 bar, at which point absorptionof the carbon dioxide commenced. The reaction is exothermic and at thecompletion thereof the temperature was 120° C. The mean velocity ofabsorption CO₂ during the reaction was 1.7 grams per minute.

The reaction resulted in the preparation of 580 grams of cyclocarbonateoligomer containing 22.7% cyclocarbonate groups and 0.1% epoxy groups.Conversion was 99%.

EXAMPLE 3

Using the procedures of Example 1, 523 grams of epoxy resin D.E.N.-431(Dow Chemical) were mixed with the catalyst tetrabutylammonium bromide(C₄H₉) ₄NBr in quantity 0.5% of weight and the epoxy/catalyst mixturewas loaded to the reactor (volume—1 liter). The carbon dioxide was fedto the reactor under a pressure of 8 bars for a period of 90 minutes.The initial temperature of the reactor was 70° C. and the finaltemperature increased to 120° C. due to the exothermic nature of thereaction. The mean velocity of absorption of CO₂ during the reaction was2 grams/min.

The reaction resulted in the preparation of 590 grams of cyclocarbonateoligomer containing 28% cyclocarbonate groups and 1% epoxy groups.Conversion was 97%.

EXAMPLE 4

Using the procedure of Example 1, 516 grams of epoxy resin D.E.R.-324(Dow Chemical) was mixed with the catalyst tetrabutylammonium iodide(C₄H₉) ₄NI in quantity of 0.5% of weight of epoxy. The epoxy/catalystmixture was then loaded into the reactor (volume—1 liter). Carbondioxide was fed to the reactor through the hollow shaft and out of theimpeller at a pressure of 1.5 bar for a period of 40 minutes. Theinitial temperature of the reactants was 70° C. and increased due to theexothermic nature of the reaction to a final temperature of 120° C. Themean velocity of absorption CO₂ during the reaction was 2.8 grams/min.

The reaction resulted in the preparation of 580 grams of cyclocarbonateoligomer containing 34% cyclocarbonate groups and 0.5% epoxy groups.Conversion was 98%.

EXAMPLE 5

Using the procedure of Example 1, 516 grams of epoxy resin D.E.R.-324(Dow Chemical) were mixed with the catalyst tetrabutylammonium chloride(C₄H₉) ₄NCl in quantity 0.5% of weight of epoxy. The epoxy/catalystmixture was then loaded into the reactor (volume—1 liter). Carbondioxide was fed to the reactor at atmospheric pressure for a period of120 minutes. The initial reactor temperature was 70° C. increased to120° C. due to the exothermic nature of the reaction.

The reaction resulted in the preparation of 500 grams of cyclocarbonateoligomer containing 34% cyclocarbonate groups and 0.3% epoxy groups.Conversion was 98%.

EXAMPLE 6

Using the procedure of Example 1, 600 grams of epoxy resin Laproxide(Russia) were mixed with the catalyst tetrabutylammonium bromide (C₄H₉)₄NBr in the quantity 0.5% of weight of epoxy. The epoxy/catalyst mixturewas then loaded into the reactor (volume—1 liter). Carbon dioxide wasfed to the reactor at a pressure of 1.5 bar for a period of 90 minutes.The initial temperature of the reactor was 70° C. and increased to afinal temperature of 120° C. due to the exothermic nature of thereaction.

The reaction resulted in the preparation of 665 grams of cyclocarbonateoligomer containing 23% cyclocarbonate groups and 0.3% epoxy groups.Conversion was 98%.

The conversion rates and reaction information of examples 1-6 aresummarized in the Table of FIG. 7 and compared with the results obtainedusing the procedures set forth in U.S. Pat. No. 5,175,312.

Network nonisocyanate polyurethanes were prepared using the synthesizedcyclocarbonates.

The Second Stage.

In the second stage of the reactor, a cyclocarbonate or an epoxy isoligomer is reacted with amino containing compound, in particular acompound containing terminated amino groups, to form “star”hydroxyurethane or epoxy oligomers with increased functionality (FIG.5-7).

Suitable terminated amino groups are those containing primary aminogroups, i.e. —NH₂ groups without radicals. In particular, polyfunctionalprimary amino-terminated oligomers of the following formula may be used:R—(NH₂)_(m)wherein

-   R is aliphatic, cycloaliphatic, ether, ester and acrylic groups, and-   m is≧3.

Any cyclocarbonate or epoxy oligomer can be used in this reaction. In apreferred embodiment of the invention, the cyclocarbonate and epoxyoligomers are cyclocarbonate or epoxy oligomers of increasedfunctionality having at least two and preferably more functional groupsin their structure. In a preferred embodiment of the invention, thefunctionality is from about 3 to about 5, and is more preferably fromabout 3 to about 4.

In one embodiment of the invention, a cyclocarbonate oligomer with threeterminal cyclocarbonate groups reacts with primary diamine as shown onthe FIG. 5 to form “star” oligomer with four or more cyclocarbonate andhydroxyurethane groups. The oligomer with two terminated epoxy groupsreacts with primary diamine as shown on the FIG. 6 to form “star”oligomer with four or more epoxy groups. On the base of “star” oligomerswith increased functionality amino adducts were prepared (FIG. 7).

The diamines used in the present invention have amine groups with equalor different reactivities. The oligomer with increased functionality hasat least average three amino groups.

The Third Stage.

The resulting urethane containing “star” oligomer can serve as ahardener for oligomers with epoxy or cyclocarbonate groups. Or “star”oligomer with terminated cyclocarbonate groups which may be cured byprimary amino oligomer (f>, =2). So we have a material (the urethanecontaining “star” oligomers with amino end groups, cyclocarbonate endgroups and epoxy end groups with increased functionality) that, have thesubstantial advantages over the prior art it has the increased strengthand elasticity.

Any cyclocarbonate or epoxy oligomer may be used.

The practical applications of this invention are very interesting. Forexample, we can produce paints, adhesives, composite compounds, etc.

The present invention provides a material that has combination is of allthe advantage of known nonisocyanate materials plus increased mechanicalproperties of polyurethane.

EXAMPLE 7

Stage II

“Star” cyclocarbonate oligomer containing hydroxyurethane groups withincreased functionality was prepared by dissolving of 2M (2268 g) ofcyclocarbonate oligomer Laprolat-803(Example 6) in 1M (170 g) ofIsophorondiamine (CREANOVA spezialchemie GmbH). This 2438 g were chargedinto the reactor, which is jacketed for temperature control. The reactorwas operated at atmospheric pressure and in several small portions,because the reaction is exothermic. The reaction is going at 80° C.during 3-4 hours.

It is also possible to prepare oligomers in presence of solvents. It ispossible to use any of diamine and cyclocarbonate compound. After allthe amine was added to the reactor samples were taken and measured foramine group concentration. The content of amine group in the finishedproduct was about 0%, indicating that amine groups had reacted withcyclocarbonate groups and we have now new “star” hydroxyurethaneoligomer with increased functionality (HUOIF).

Stage III

The urethane containing “star” oligomer from the stage I was reactedwith Isophorondiamine (ISPhDA) and resulted in the formation of anelastomer with a tensile strength 1.5 Mpa and an elongation at break of250% as measured by ASTM D638884.

EXAMPLE 8

Stage II

“Star” cyclocarbonate oligomer with increased functionality was preparedby dissolving of 3M of cyclocarbonate oligomer (3402 g) Laprolate-803(Example 6) in 2M of isophorondiamine (Creanova specialchemie GmbH) −340g. This 3742 g were charged into the reactor. The process is as stage 1(Example 7).

Stage III

The urethane containing oligomer from the stage I was combined withIsophorondiamine (ISPhDA) to form elastomer with Tensile strength 0.7Mpa and Elongation at break 300%.

EXAMPLE 9

Stage II

“Star” cyclocarbonate oligomer with increased functionality (CCOIF) wasused from stage 1 (Example 7) for preparing “star” amino containinghydroxyurethane oligomer with increased functionality (AHUOIF).

AHUOIF was prepared by dissolving of 1M (2438 g) CCOIF from the stage 1(Example 7) in 8M (1360 g) ISPhDA. The reactor was operated atatmospheric pressure and into several small portions. The reaction isgoing at 80° C. during 2-3 hours. Total 3798 g. The “star” epoxyoligomer with increased functionality EOIF was prepared by dissolving of4M (1200 g) of Polypox R-14 (neopentylglycoldiglycidyl ether, UPPC GmbH)in 1M (170 g) of ISPhDA. The reaction is going at 80° C. during 1-2hours.

Stage III

The urethane containing oligomer AHUOIF and epoxy oligomer EOIF fromstage I was combined with 8M (2400 g) Polypox R-14 to form elastomerwith Tensile strength 11 Mpa and Elongation at Break 90%.

EXAMPLE 10

Stage II

The AUOIF was used from stage I (Example 9).

The EOIF was used from stage I (Example 9).

Stage III

The urethane containing oligomer HUOIF and epoxy oligomer EOIF fromStage I was combined with 4M (1200 g) of Polypox R-14 to form elastomerwith Tensile strength 9 Mpa and Elongation at Break 120%.

A comparison of the network polyurethane properties of examples 7-10 aresummarized in the Table 2 of FIG. 8 and compared with the resultantpolyurethane obtained using the procedures set forth in U.S. Pat. No.5,175,312.

EXAMPLE 11

Stage I

An acrylic cyclocarbonate oligomer was prepared using the procedures andequipment of example 1, 425 grams of acrylic epoxy resin Setalux 17-1433(60%) (Akzo Nobel) was mixed with 0.25% by weight of epoxy of atetrabutlyammonium bromide catalyst (C₄H₉)NBr. The epoxy/catalystmixture was loaded into the reactor (volume—1 liter). Carbon dioxide wasfed under a pressure of 8 bar for 180 minutes. The reaction began at 70°C. and due to the exothermic nature of the reaction ended at atemperature of 120° C.

The reaction resulted in the preparation of 447 grams of an acryliccyclocarbonate oligomer with 13% cyclocarbonate groups and 0.4% epoxygroups. Conversion was 96%.

Stage II

The amineurethane oligomer with increased functionality (AUOIF) wasprepared by dissolving 2M (1170 g) of cyclocarbonate of Polypox R-20(UPPC) previously synthesized in the reactor using the procedures ofExample 6 in 1M (170 g) of Isophorondiamine (Creanova spezialchemieGmbH). The 1340 g mixture of cyclocarbonate in diamine was charged intothe reactor, which was jacketed for temperature control. The reactionwas conducted at 80° C. for 3 hours, during which an additional 8M (1326g) of Isophorondiamine was added. The reaction yielded 2700 g of AUOIF.

Stage III

669 g of the acrylic cyclocarbonate oligomer from stage I and 225 g ofthe AUOIF from stage II were combined by stirring at room temperature toform a liquid that was coated on a metal substrate at a thickness of 50mkm. The coated substrate was cured for 2 hours at a temperature of 100°C. to form a UV-stable coating. The hardness of the cured coating was H,the impact (face) was 50 kg.cm.

EXAMPLE 12

Stage III

669 g of the acrylic cyclocarbonate oligomer from stage I of Example 11and 81 g of 100% Vestamine TMD (Creanova) were combined by stirring atroom temperature to form a liquid that was coated on a metal substrateat a thickness of 50 mkm. The coated substrate was cured for 2 hours ata temperature of 110° C. to form a UV-stable coating. The hardness ofthe cured coating was H, the impact (face) was 50 kg.cm.

EXAMPLE 13

Stage II

A synthesis of a cyclocarbonate with a tertiary amine group containingcompound was conducted.

A cyclocarbonate based upon Eponex 1510 (Shell) was prepared using theprocedures and conditions of Example 6. 562 g of the resultantcyclocarbonate was mixed with 146 grams ofN,N-bis(3aminopropyl)methylamine (BASF). The resultantcyclocarbonate/amine mixture was charged into the reactor, which wasjacketed for temperature control. The reaction was conducted at 100° C.for a period of 2-3 hours and yielded 708 g of an amino containingoligomer.

Stage III

The 708 g of the amino containing oligomer from stage II and 1340 (100%)acrylic epoxy resin Setalux 17-1433 were combined by stirring at roomtemperature to form a liquid that was coated on a metal substrate at athickness of 50 mkm. The coated substrate was cured for 1 hour at atemperature of 100° C. to form a UV-stable coating. The hardness of thecured coating was H, the impact (face) was 50 kg.cm.

1. An improved method of synthesizing a cyclocarbonate from an epoxycompound and carbon dioxide at low pressure and temperature in areactor, the method comprising the steps of: a) supplying a catalyst tothe reactor; b) introducing the epoxy compound to thecatalyst-containing reactor to create a reactionary mass in the reactor;and c) feeding carbon dioxide to the reactor i) via a first gas inletinto the head space above the reactionary mass, and, substantiallysimultaneously, ii) directly into the reactionary mass through a turbinemixing device comprising a shaft with a hollow interior associated witha gas entrainment impeller directly into the reactionary mass, saidshaft having a second gas inlet in fluid communication with the headspace and said impeller being in fluid communication with the shaftinterior and being positioned within the reactionary mass, said impellerfurther having peripherally disposed gas dispersion ports suitable forintroducing gas into the reactionary mass, whereby iii) upon rotation ofthe shaft and the associated impeller carbon dioxide is drawn into theshaft interior from the head space via the second inlet and isintroduced via the dispersion ports into the reactionary mass, thereactionary mass being saturated with the carbon dioxide and reacting toform the cyclocarbonate, said reaction taking place in the absence ofreactant solvents and substantially without generation of foam.
 2. Themethod of claim 1, wherein the epoxy compound is selected from the groupconsisting of aromatic epoxies, aliphatic epoxies, cycloaliphaticepoxies and acrylic epoxies.
 3. An apparatus for producingcyclocarbonates from epoxy compounds and carbon dioxide at reducedpressure, time, and temperature, the apparatus comprising: a) a reactorvessel having an inlet for supplying a catalyst and the epoxy compoundsthereto, wherein the catalyst and epoxy compound form a reactionarymass, and a first gas inlet for supplying the carbon dioxide to a headspace above the reactionary mass; and b) a turbine mixing device locatedin the reactor vessel, the turbine mixing device comprising a shaft witha hollow interior associated with a gas entrainment impeller, said shafthaving a second gas inlet in fluid communication with the head space andsaid impeller being in fluid communication with the shaft interior andbeing positioned within the reactionary mass, said impeller furtherhaving peripherally disposed gas dispersion ports suitable forintroducing gas into the reactionary mass, whereby upon rotation of theshaft and the impeller carbon dioxide is drawn into the shaft interiorfrom the head space via the second inlet and is introduced via thedispersion ports into the reactionary mass.
 4. A non-polyester staroligomer selected from the group consisting of star epoxy oligomershaving at least three epoxy groups and no more than about 1.0% by weightof terminal cyclocarbonate groups, star cyclocarbonate oligomers havingat least three cyclocarbonate groups and no more than about 1.0% byweight of terminal epoxy groups, star hydroxyurethane oligomers havingat least three hydroxyurethane groups, and star aminohydroxyurethaneoligomers having at least three aminohydroxyurethane groups.
 5. The staroligomer of claim 4, wherein said oligomer has a functionality greaterthan
 2. 6. The star hydroxyurethane oligomer according to claim 4,wherein the oligomer comprises at least one hydroxyurethane linkage. 7.The star aminohydroxyurethane oligomer according to claim 4, wherein theoligomer comprises at least one hydroxyurethane linkage.
 8. A method ofsynthesizing a non-polyester star nonisocyanate network polyurethane bycross-linking a star cyclocarbonate having at least three cyclocarbonategroups with a bi-functional amine oligomer having a functionality of atleast about 2, at least one of said star cyclocarbonate and said amineoligomer containing a hydroxyurethane linkage.
 9. A method of preparinga non-polyester foam star nonisocyanate network polyurethane, comprisingthe steps of: a) cross-linking a star cyclocarbonate with abi-functional amine oligomer having a functionality of at least about 2;and b) adding a blowing agent.
 10. The method of claim 9, wherein theblowing agent is pentane.
 11. A method of preparing a non-polyester starcyclocarbonate oligomer having at least three cyclocarbonate groups andno more than about 1.0% by weight of terminal epoxy groups, comprisingthe step of: reacting about x moles of a primary diamine with about ymoles of a cyclocarbonate oligomer in at least one step to form a starcyclocarbonate oligomer of increased functionality, wherein X≧1, y≧2,y>x.
 12. The method of claim 11, wherein the primary diamine is selectedfrom the group consisting of substantially linear aliphatic primarydiamines, primary diamines comprising alicyclic groups, and mixturesthereof.
 13. A method of preparing a non-polyester star epoxy oligomerhaving at least three epoxy groups and no more than about 1.0% by weightof terminal cyclocarbonate groups, comprising the step of: reacting atotal of about x moles of a primary diamine with y moles of an epoxyoligomer in at least one step to form a star epoxy oligomer of increasedfunctionality, wherein x≧1, y≧2, y>x.
 14. The method of claim 13,wherein the primary diamine is selected from the group consisting ofsubstantially linear aliphatic primary diamines, primary diaminescomprising alicyclic groups, and mixtures thereof.
 15. A method ofpreparing a non-polyester star aminohydroxyurethane oligomer having atleast three aminohydroxyurethane groups, comprising the step of:reacting a star cyclocarbonate oligomer having at least threecyclocarbonate groups and a hydroxyurethane linkage with a primarydiamine.
 16. The method of claim 15, wherein the primary diamine isselected from the group consisting of substantially linear aliphaticprimary diamines, primary diamines comprising alicyclic groups, andmixtures thereof.
 17. A method of synthesizing a non-polyester acrylicnonisocyanate network polyurethane by cross-linking an acryliccyclocarbonate having at least three cyclocarbonate groups with abi-functional amine oligomer having a functionality of at least about 2.18. A method of preparing a non-polyester foam acrylic nonisocyanatenetwork polyurethane comprising the steps of: a) cross-linking anacrylic cyclocarbonate having at least three cyclocarbonate groups witha bi-functional amine oligomer having a functionality of at least about2; and b) adding a blowing agent.
 19. The method of claim 18, whereinthe blowing agent is pentane.
 20. A method of preparing a non-polyesteracrylic cyclocarbonate oligomer having at least three cyclocarbonategroups, comprising the step of: reacting an acrylic epoxy resin withcarbon dioxide in the presence of a catalyst.
 21. A method of preparinga non-polyester acrylic aminohydroxyurethane oligomer comprising thestep of: reacting an acrylic cyclocarbonate oligomer having at leastthree cyclocarbonate groups with a primary diamine.
 22. The method ofclaim 21, wherein the primary diamine is selected from the groupconsisting of substantially linear aliphatic primary diamines, primarydiamines comprising alicyclic groups, and mixtures thereof.
 23. Anon-polyester star noniso-cyanate network polyurethane in the form of afoam or a UV stable coating.
 24. A method of preparing a non-polyesterstar cyclocarbonate oligomer having no more than about 1.0% by weight ofterminal epoxy groups by reacting about 1 to about 2 moles of primarydiamine with about 2 to about 3 moles of the compound of the formuladepicted in FIG. 9, whereinR=H, CH₃ or C₂H₅,R′=CH₂Cl or CH₃,n=1,2 or 3, and m1, m2 and m3 are independently selected over the rangefrom 3 to 12 inclusive such that the molecular weight of the starcyclocarbonate oligomer is about 600-1600.
 25. A non-polyester acrylicnonisocyanate network polyurethane in the form of a foam or a UV stablecoating.
 26. The method of claim 1, wherein the reaction is completedwithin a period of about 40-120 minutes.